Insecticidal compositions and methods of killing insects using alpha,beta-dioxohydrocinnamonitriles

ABSTRACT

1. A METHOD FOR CONTROLLING INSECTS COMPRISING APPLYING TO SAID INSECTS AN INSECTICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA:   R,R1,R3-PHENYL-NH-N=C(-CN)-CO-R2   WHEREIN R IS HALO, ALKYL OF TO 4 CARBONS, ALKOXY OF 1 TO 4 CARBONS, CYANO NITRO, TRIFLUOFOMETHYL OR P-CHLOROPHENOXY; R1 IS HYDROGEN, HALO, TRIFLUOROMETHYL OR ALKYL OF 1 TO 4 CARBONS; R2 IS 2-FURYL; AND R3 IS HYDROGEN OR HALO.

United States Patent INSECTICIDAL COMPOSITIONS AND METHODS OF KILLING INSECTS USING oc,)3-DIOXOHYDRO- CINNAMONITRILES Donald Perry Wright, Jr., Pennington, Donald Frederic Barringer, Jr., Trenton, and Donald Edward McKay, Highland Park, N.J., assignors to American Cyanamid Company, Stamford, Conn.

No Drawing. Application May 4, 1972, Ser. No. 250,338, now Patent No. 3,793,456, dated Feb. 19, 1974, which is a continuation-in-part of abandoned application Ser. No. 141,444, May 7, 1971. Divided and this application Nov. 8, 1973, Ser. No. 414,054

Int. Cl. A01n 9/20, 9/28 US. Cl. 424-285 6 Claims ABSTRACT OF THE DISCLOSURE The present invention relates to insecticidal methods and compositions employing cc-fi-diOXOhYdI'OCiIJHEIHIOIIitriles having the formula:

0 ill-R2 where R, R R and R are defined as follows: R is halo, loweralkyl (C -C loweralkoxy (C -C cyano, nitro, trifluoromethyl, phenylazo or p-chlorophenoxy; R is hydrogen, halo, trifluoromethyl or loweralkyl (C -C R is hydrogen or halo; and R is phenyl, halophenyl, dihalophenyl, alkyl (C -C phenyl, loweralkoxy (C -C phenyl, l-naphthyl, 2-furyl, or 2-thienyl.

This application is a divisional of our co-pending application, Ser. No. 250,338, filed on May 4, 1972, now US. Pat. 3,793,456, issued Feb. 19, 1974; which is a continuation-in-part application Ser. No. 141,444 filed May 7, 1971 now abandoned.

The present invention relates to the use of certain hydrazones in insecticidal methods and compositions. It further relates to certain novel hydrazones used therein and to the preparation thereof.

More particularly, the invention relates to insecticidal methods and compositions employing hydrazones of afidioxohydrocinnamonitriles having the formula:

where R, R R and R are defined as follows: R is halo, loweralkyl (C -C loweralkoxy (C -C cyano, nitro, trifluoromethyl, phenylazo or p-chlorophenoxy; R is hydrogen, halo, trifluoromethyl or loweralkyl (C -C R is hydrogen or halo; and R is phenyl, halophenyl, dihalophenyl, alkyl (C -C phenyl, loweralkoXy (C -C phenyl, l-naphthyl, 2-furyl, or Z-thienyl. It further relates to the novel hydrazone compounds thereof having unexpectedly high insecticidal activity, having the formula.

NHM

3,840,687 Patented Oct. 8, 1974 ice wherein Y is hydrogen, chloro or loweralkyl (C -C n is O, l or 2; and m is 1 or 2. Especially preferred compounds therein are: oc,fl-diOXO-, 11-:(3 chloro o tolyl) hydrazone]hydrocinnamonitrile, 00,5 dioXo-, oz [(3,4- dichlorophenyl)hydrazone]hydrocinnamonitrile, 0:,5 di- OXO, a [(2,4 dichlorop-henyl) hydrazone]hydrocinnamonitrile, p-chloro 11,5 dioxo-, a-[(p-chlorophenyl) hydrazone]hydrocinnamonitrile and a,p-dioxo-, a-[(2,4,5- trichlorophenyDhydrazone]hydrocinnamonitrile. Finally, it relates to the preparation of the above novel hydrazone compounds.

Illustrative hydrazones include:

hydrocinnamonitrile, a,fl-dioxo-, a-[(2,5-dichlorophenyl) hydrazone];

hydrocinnamonitrile, a,/3'-dioxo-, a-[(p-chlorophenyl)- hydrazone];

hydrocinnamonitrile, a,,B-dioxo-, u-[(p-phenylazophenyl) hydrazone];

hydrocinnamonitrile, oc,]3-dlOXO-, a-[(3,4-dich1orophenyl) hydrazone];

hydrocinnamonitrile, afi-dlOXO-ot- 2,5 -dichlorophenyl) hydrocinnamonitrile, a,/3-di0XO-, a-[(m-chlorophenyl) hydrazone];

hydrocinnamonitrile, a,fldiOXO-, a-[(o-chlorophenyl) hydrazone];

hydrocinnamonitrile, a,/3-di0XO-, u-[(4-chloro-o-tolyl) hydrazone];

hydrocinnamonitrile, 0a,;3-dlOXO-. a-[(2,5-dichlorophenyl) hydrazone];

hydrocinnamonitrile, p-chloro-u,,B-dioxo-, a-[(p-chlorophenyl)hydrazone] and the like.

The hydrazones are prepared by reacting an aniline of Formula II with a diazotizing agent in the presence of a mineral acid and further reacting the thus-formed diazonium salt with an aroylacetonitrile 111. The synthetic method may be illustrated as follows:

i R3 R C-R 1 R4N0z EX 3 -NH2 NHN=O 2 RzCOCHiCN R1 R1 CN 11 III 1 wherein R is selected from the group consisting of an alkali metal, such as lithium, potassium or sodium and C -C loweralkyl groups, such as methyl, ethyl, n-propyl,

iso-propyl, n-butyl, t-butyl and the like and HX represents a mineral acid, such as HCl, H 80 HNO and the like. R, R R and R are as above.

The relative quantities of the ingredients employed can be widely varied. For optimum yields, it is generally preferred to react equimolar quantities of the aniline and nitrite. Lower alcohols C -C water and mixtures thereof are among the preferred solvents for use in carrying out the synthesis. It is also preferred to employ a mineral acid in suflicient quantities to produce an acidic pH in the aqueous or alcoholic solvent and to adjust the reaction temperature to temperatures within the range of from about -10 C. to about +10 C. The preferred temperature is about C.

Sodium and potassium nitrite and methyl, ethyl or nbutyl nitrite are among the preferred diazotizing agents which are particularly well suited for use in the syntheses.

Preferred mineral acids include sulfuric, hydrochloric and hydrobromic acid. It is generally preferred to employ a slight excess of the acid over and above the stoichiometric amount required to form the substituted benzene diazonium salt.

After formation of the desired diazonium salt, the reaction mixture is preferably reacted further by adding it to a mixture of the appropriate aroylacetonitrile and a weak base, such as sodium or potassium acetate while the temperature is maintained at from about 10 C. to about +10 C. The desired hydrazone of the u, 8-dioxohydrocinnamonitrile is produced thereby and may be recovered from the reaction mixture by any convenient means, such as, by filtration, centrifugation and the like.

It has been found that the hydrazones of Formula I and especially the novel hydrazones a,,BdiOXO-, a-[(3- chloro-o-tolyl)hydrazone] hydrocinnamonitrile and 0:,B- dioxo-, oz [(3,4 dichlorophenyl)hydrazone1hydrocinnamonitrile are useful as insecticides. They are particularly effective for controlling lepidoptera and mosquitoes, especially in the larval stages.

The insecticidal methods of the present invention involve contacting the insect to be controlled or the locus or area where insect control is desired with an insecticidally effective amount of one or more of said hydrazones. Application of the active ingredient at a rate of from between about 0.5 and about 15 pounds per acre of the active ingredient is generally sufiicient to achieve the desired insect control.

For application of the hydrazones, it is generally preferred to employ them in combination with conventional pesticidal adjuvants and formulation aids. They may be advantageously employed with the use of either solid or liquid adjuvants and applied in the form of dusts, dust concentrates, Wettable powders, emulsifiable concentrates and the like.

Field application of these formulations may be made by conventional equipment, such as power dusters, boom and hand sprayers, spray dusters, addition to irrigation water, and the like.

The active ingredient may be initially formulated with a concentrated composition, comprising the active ingredient in a solid or liquid adjuvant which serves as a formulation aid or conditioning agent, permitting the concentrates to be further mixed with a suitable solid or liquid carrier.

Useful liquid adjuvants in which the toxicant is dissolved, suspended or distributed include, for example, xylene, benzene, lower alcohols C -C fuel oil or the like, with or without an emulsifying agent. For application, the resulting solution can be further diluted with either water or an organic diluent, such as deodorized kerosene. Concentrations in the range of from about to about 95% are generally suitable for initial solution. When diluted for application, suitable solutions may contain the active ingredient in concentrations of from about 0.5 ppm. to about 5000 p.p.m.

Suitable solid adjuvants include, for example, attapulgite, kaolin, talc or diatomaceous earth in granular or finely ground form. The active ingredient can be conveniently formulated with the solid adjuvants as dusts, dust concentrates, Wettable powders, granulars and the like.

Dusts are generally prepared by grinding together from about 1% to 10% by weight of the hydrazone with a finely divided inert diluent such as attapulgite, kaolin, diatomaceous earth, talc, or fullers earth. These formulations can then be applied with dusting equipment to the foliage of agronomic crops or fields, meadows, forests or the like which are to be protected from insect attack or where insect control is desired. Application is generally sufiicient to provide between about 0.5 and 15 pounds per acre of active material.

Dust concentrates are usually prepared in the same manner as dusts but generally from about 25% to 75% by weight of the active hydrazone and from 75% to 25% by weight of diluent are used.

Wettable powders are prepared in the same fashion as the dust concentrates, however, from about 1% to 5% by weight of an emulsifying agent and from about 1% to 5% by Weight of a dispersing agent are usually included in such formulations. Polyethylene glycols, methoxy polyethylene glycols, sodium lignosulfonate, calcium dodecylbenzene sulfonate and the like are among the emulsifying agents and dispersing agents which can be used in these formulations. In practice, the Wettable powders are generally dispersed in water and applied as a dilute spray to the vegetation or water where insect control is desired.

Usually, concentrations of the active ingredient of from about 10 ppm. to 1000 ppm. dispersed in the water of ponds, lakes, creeks, swamps and such will give excellent control of mosquito larvae. Excellent insect control and plant protection in fields, forests, crop lands and the like is generally achieved by application of the active ingredient at rates of from about 1 to about 15 pounds per acre.

The invention is further illustrated by the following examples which are not to be taken as limitative thereof. In each case, the parts and percentages are by Weight un less otherwise indicated.

EXAMPLE 1 Preparation of a,B-Dioxohydrocinnamonitrile u- (a,a,a,a,a',a-hexafluoro-3,5-xylyl)hydrazone GO-CHr-CEN The a,ot,oc,ot',oc',cc' hCXaflLIOIO 3,5 xylidine (5.72 g., 0.0250 mole) was added to 25 ml. of a stirred, ice-cold 6N-sulfuric acid solution. The hydrosulfate salt precipitated as a fiocculent white solid. This mixture was stirred and maintained in an ice bath while a solution of-the sodium nitrite (1.72 g., 0.0250 mole) in a little water was added dropwise. The yellow diazonium salt solution was then filtered to remove a small amount of precipitate. The p-oxohydrocinnamonitrile (3.62 g., 0.0250 mole) was slurried in 25 ml. of 2B ethanol, and a solution of sodium acetate (12.30 g., 0.150 mole) in 40 ml. of water; was

added. This mixture was stirred and maintained in an ice bath while the diazonium salt solution was added dropwise. Thereafter, the solution was stirred with cooling for an additional hour and the desired product produced as 6 EXAMPLE 18 Preparation of a,B-DiOXO-, a-[(3-Chloro-o-tolyl)hydrazone]hydrocinnamonitrile a solid precipitate was recovered by filtration. It was Step 1 washed with water, and air dried to yield 8.07 g. (84% 5 C1 (3H1 01 yield) in the form of a yellow-orange solid having an m.p. of 185 C.191 C. The product was purified and NH2+HC1+KN02 NENQCIG recrystallized from ethanol with a little added water to yield 5.93 g. (62%-) of a yellow-orange solid having an 141's 1891 m.p. of l9l.0 C.193.5 C. Identification was by infra- Step 2 red spectrum and the following elemental analysis: 01 cm Calcd. for C H F N O: C, 53.00; H, 2.35; F, 29.59; 9 N, 10.91. Found: C, 52.77; H, 2.33; F, 30.55; N, 10.92. NEN Cl EXAMPLES 2-16 1891 Preparation of Various a, 8-Dioxohydrocinnamonitrile MeOH/OzO HydrazoneS QC OCHQQEN NaOAc A variety of a,fl-dioxohydrocinnamonitrile hydrazones 145.2 82 of Formula I were prepared by the general procedure of Example 1, employing the appropriately substituted ani- OTfiJ=NTNHQ line and cinnamonitrile, in lieu of the a,,a,a',a',a-hexa- (EN I fluoro 3,5 xylidine and fi-oxohydrocinnamonitrile used therein, to produce the hydrazones set forth in Table I 297-2 below. R which is in Table I, is in each case H. 5.66 Grams (0.04 m.) of 3-chloro-o-toluidine was dis- TABLE I Calculated Found Example Percent Melting number R R1 R2 yield point C.) C H N 01 C H N Cl 2 B81120 Phenyl 43 145. 5-148.0 76.24 4.38 14.04 76.53 4.44 14.11 H do 87.5 165-165.5 63.50 3.55 14.81 12.50 63.70 3.75 14.72 12.50 H -d6 92 126. 5-127.5 63.50 3.55 14.81 12.50 63.41 3.58 14.78 12.48 o-CH; ..do 89 156.5-157 64.54 4.06 14.11 11.91 64.75 4.15 14.17 11.97 501 .do 88 127-1275 56.62 2.85 13.20 22.29 55.68 3.40 12.22 20.73 H p-Chlorophenyl--- 226-2281 56.62 2.85 13.20 22.29 56.51 2.90 13.18 .41

H Phenyl 250-251 67.48 5.03 17.49 67.30 4.97 17.52

H 2-iuryl 83 172. 5-173 57.05 2.95 15.36 12.95 57.06 2. 96 15.39 13.09 H 24111611 1-.. 86 220-2205 53.89 2.78 14.50 12.24 55.41 2.96 14.89 12. 46 H l-naphthyl 54 174-175 68.37 3.63 12.59 10.62 69.14 3.70 12.48 10.69 6-CHa Phenyl 11 88 175-1755 63.48 3.56 14.82 12.50 63.41 3.67 4.89 13.08 00m o-NOz 96 182-183 59.26 3.73 17.28 59.01 3.83 17.54 Phenylazo H 83 179-180 71.37 4.28 19.82 71.03 4.06 19.66 16- 200113 501 84 191-193 61.25 3.85 13.39 11.30 61.16 3.72 12.94 11.26

1 Decomposes.

EXAMPLE 17 solved in ml. of 3N HCl (0.186 m.), and the solution was cooled to 0 C. 3.6 Grams 0.04 m. of otassium Preparatlon of 3: 1 henynhydra nitrite, which was dissolved in 10 ml. of v aten was then zone} y ocmnamom n 6 added dropwise, maintaining the temperature at 0 C. 55 The diazonium salt solution was then added to a solution C1 -NHN=C of 5.81 grams (0.04 m.) of benzoylacetonitrile and 30 Q grams (0.365 m.) of sodium acetate dissolved in 300 ml. 3 of water and 200 ml. of methanol, over approximately 5 minutes with rapid stirring at room temperature. The A solutio Of p-ch oa fi g H1016) in 30 60 mixture was stirred for one hour at room temperature, and ml. of 10% aqueous hydrochloric acid was cooled to the bright yellow solids were collected by filtration. The -5 C., and a solution of sodium nitrite (1.5 g., 0.02 crude product was recrystallized from 300 ml. of ethanol mole) in 5 ml. of water was added dropwise. The resultto 50 ml. of methyl ethyl ketone, water was added at ing solution was stirred for V2 hour. Excess nitrous acid reflux until the cloud point was reached (approximately was destroyed by addition of sulfamic acid, and the result- 50 ml. necessary). 9.45 Grams theory) of yellow ing solution was filtered. The filtrate was added dropwise needles were obtained. Melting point is 133 C. to over a period of 15 minutes to a mixture of benzoylaceto- 133.5 C. nitrile (2.9 g., 0.02 mole) in 30 ml. of methanol, 10 ml. Analysis Calculated for N OClC H C, 64.56; H, of water, and 15 g. of solid sodium acetate at 0 C. The 4.03; N, 14.12. Found: C, 64.16; H, 4.00; N, 14.08. resulting mixture was stirred overnight. The desired prod- As in the case of the preparation of a,B-diOXO-, (it-[(3- uct was isolated by filtration, washed with water, and dried ehloro-o-tolyl)hydrazone] hydrocinnamonitrile, the other in vacuo at 80 C., yielding 5.0 g. (88%). novel hydrocinnamonitri'le insecticides mentioned above,

Purification was effected by successive recrystallizations e.g., a,fl-diOXO-, a-[(3,4-dichlorophenyl)hydrazone hydrofrom aqueous ethanol to give a product having an m.p. cinnamonitrile, can also be prepared by reacting the apof C.175.5 C. 75 propriately substituted aniline at a temperature of from 7 about 10 C. to about +10 C. with a compound of the formula R NO in a solvent rendered acidic by the addition of a mineral acid to form a diazonium salt solution of said aniline, and reacting the diazonium salt in solution to form said hydrazone by adding said diazonium salt to a mixture of a weak base and an aroylacetonitrile, e.g.,

wherein R is a member selected from the group consisting of alkali metals and -0 loweralkyl groups.

EXAMPLE 19 Preparation of Various u,,B-Dioxohydrocinnamonitrile Hydrazones A variety of a,fi-dioxohydrocinnamonitrile hydrazones of Formula I were prepared by the general procedure of Example 1, employing the appropriately substituted aniline and cinnamonitrile. The compounds produced are set forth in Table 11 below.

TAB LE II Rs 1R2 NHN=0 Melting point R R1 R3 R2 0 2-01 3-01 H 153-154 2-01 4- 01 H 162-163 2-01 6-01 H 158-155 3-01 4-01 H 186-188 3-01 5-01 H 204- 208 4-Br H H 180-182 4-0N H H 244-248 4-0Ha H H 157-158 4-n-04Ho H H 115-116 -CH3 5-i-C3H7 H 128-130 2-0H3 5-01 H 119-120 3-0Ha 4-F H 151-154 3-01 4-0H3 H .....de 179-180 4-01 H H 3-chloropheny 214-216 2-01 4-01 H 4-ch10ropheny1. 175-177 3-01 4-01 H 2-01 5-01 H 3-chlorophenyl- 3-01 4-01 H 2-0H3 3-01 H o 3-01 4-0] H 2,4 dichlorophenyl 4-0 OH; H H 4-chlorophenyl 4-N0g H H do 3-NO H H do 4-01 H H 4-t-butylpheny1. 172-174 3-01 4-0l H do 177-178 4-01 H H 4-methoxyphenyl... 181-182 3-01 4-01 H do 191-192 2-01 4-01 6-01 2-01 4-01 5-01 3-CF3 5-0F3 H 4-ClCsHa0 H EXAMPLES 20-33 The insecticidal activity of the compounds of Formula I is demonstrated by the following tests using the test procedures set forth below.

Southern Armyworm (Pradenia eridania Cram.)

Compounds to be tested are made up as 0.1% solutions in 65/35 acetone-water mixtures. Sieva lima bean leaves are then dipped in the selected test solution and set in a hood to dry. When dry, they are placed in petri dishes lined on the bottom with a moist filter paper and ten third-instar armyworms are added to each dish. The dishes are covered, held at 80 F., 60% relative humidity for two days and then examined and mortality counts made. Untreated leaves are used as controls.

Tobacco Budworm (H eliothis vireseus) Compounds to be tested are made up as 0.1% solutions in 65/ 35 acetone-water mixtures. Small leaves from cotton plants are then dipped in the selected test solutions and air dried. After drying, they are placed in a small medicine cup with a dental wick saturated with Water and one third-instar tobacco budworm and held in a constant temperature and humidity room for three days. At the end of the holding period all cups are examined and mortality counts made. At least ten replicates per test solution are used.

The data obtained are in each case set forth in Table III below. R which is unshown in Table IH, is in each case H.

10 TABLE III Percent control Southern Tobacco armybudworm, WORLD, 0011- 00110811- Ex. centration tration No. R 0.1% 0.1%

33-. grhen iazo 100 100 EXAMPLES 34-42 The larvicidal activity of the compounds of Formula I is demonstrated in the following tests using mosquito larvae. The test procedure is as follows:

Mosquito Larvae (Anopheles quadrimaculatus Say) 3 Groups of 25 larvae of the common malaria mosquito are transferred with a medicine dropper to a 50 ml. beaker containing 25 ml. of water. The test compound is formulated as an emulsion containing 0.1 gram of test material, 0.2 gram of Alrodyne 315 emulsifier, a nonionic polymeric emulsifier by Alrose Chemical Company, 10 ml. of acetone and ml. of water. This 1000 p.p.m. emulsion is diluted ten-fold with 65% acetone-35% water to give p.p.m. One milliliter of the 100 p.p.m. emulsion is pipetted into 225 ml. of water in a 400 ml. beaker and stirred vigorously. The larvae in 25 ml. of water are added, giving a concentration of 0.4 p.p.m. Mortality counts are made after 24 hours at 80 F. Data obtained are provided below in Table IV. R which is unshown in Table IV below, is in each case H.

TABLE IV Percent kill mosquito larvae, concentra- Example number tion 0.4%

EXAMPLE 43 Foliar Residual Activity of Phenylhydrazones The foliar residual activity of the phenylhydrazones and commercial standards is shown in Tables V, VI, VII and VIII. The rates in all the tables are expressed in pounds of actual ingredient per acre. All materials formulated as wettable powders (WP) and emulsifiable concentrates (EC) were applied in 86 gallons of water per acre. Application was made by a single flat-top nozzle moving on an overhead track. Materials formuluated in 64.5% acetone, 35% water, and 0.5% Alrodyne 315, a

polyethylene glycol fatty ester non-ionic surfactant by Geigy Chemical Corporation were applied in the formulation vehicle at an equivalent of 86 gallons per acre. Following application, the treated plants are placed on greenhouse benches and permitted to dry. At various time intervals thereafter, treated leaves are removed from the plants, placed in petri dishes with moist filter papers on the bottoms thereof and containing or southern armyworms or gypsy moth larvae. Mortality counts are made after three days of exposure.

For bioassays with tobacco budworms, the excised leaves are cut into five sections, and each section is placed in a One-ounce plastic medicine cup containing a one-inch dental wick saturated with 'water, and one-third Instar tobacco budworm. Mortality counts are made after three days of exposure.

TAB LE V [Foliar residual activity of phenylhydrazones on lima been plants bioassayed with southern armyworms] Formation Structure Rate Percent mortality after age of residue pounds on plants ot per acre 0 wks. 2 wks. 3 wks. 4 wks.

C O-Z=N-NH -Cl 1 100 100 100 100 50% 01 r :33 as 122 N at 50% WP M 100 100 95 90 Cl-C OC=NNH-Cl 1 100 100 100 100 50% WP check 0 50% WP (BEN Cl M 80 @o 0C=NNH 1 50% (HQ-C OC=N-NH i 133 g8 28 Q 50% WP ch 0 TABLE VI [Foliar residual activity of phenylhydrazones on lima bean plants bioassayed with southern armyworms] Rate Percent mortality after age of residue pounds on plants of- Formulation Structure e 0 wks. 1 wks. 2 wks. 3 wks.

64.5 A 35 W 0.5 Alrod e315. 16 100 78 93 73 @COC=NNH 1 100 5a 25 l N JJEN l 50% WP GIG-c o-c=NNH--01 50% WP ch Foliar residual activity of phenylhydrazones on cotton plants bioassayed with tobacco budworms V 90 50 0 64.5% A, 35% W, 0 5% Alrodyne 315 C 0 Cl} N NH 12 100 mo 40 CH: Cl

TABLE VI-Continued Rate Percent mortality after age of residue pounds on plants oi per Formulation Structure acre wks. 1 wks. -2 wks. 3 wks. D 0 C l 80 40 l 1 90 so C EN l C N C1 50% WP ya 70 60 70 10 Cl C O?':=NNH Cl 1 90 100 100 20 [Foliar residual activity of experimental insecticides and standard on lirna bean, radish, and tobacco plants aged in the greenhouse and bioassayed with southern armyworms] Percent mortality of southern armyworms after 3 days of exposure Age of residue on plants in weeks Rate pounds Lima bean plants Radish plants Tobacco plants Formulaper tion Structure acre 0 1 2 3 *4 0 1 2 3 *4 0 1 2 3 .4 50%WP.- 50 63 -100 70 100 65 95 100 100 98 80 100 COC=N-NH 1 100 85 88 88 80 100 100 100 100 100 Hz Cl %WP 01 M 100 63 68 33 100 90 100 80 85 100 100 100 .73 93 1 100 98 100 73 100 100 95 100 100 01 50% WP $6 100 100 85 90 100 100 100 100 95 100 100 100 98 85 -COC=NNH Cl 1 100 100 98 83 60 100 100 100 100 100 tEN Cl C1 50% WP... y; 100 83 83 48 60 100 100 100 95 85 100 100 100 100 100 C1 CO-Z=N-NH C1 1 100 100 100 95 95 100 100 100 100 100 EN r Southern armyworms small, had to use second instar instead of third.

- TABLE VIII Foliar residual activity of experimental insecticides and standards on co! ton plants aged in the greenhouse and bioassayed with various insects Percent mortality after 3 days of exposure 50% WP $6 100 88 78 63 90 100 100 100 100 95 100 100 100 98 93 -CO((Lj=NNH- Cl 1 100 100 100 95 90 100 100 100 100 100 Age of residue on plants in weeks Rate pounds Tobacco budworm Southern amiyworm Gypsy moth larvae Formulapet tion Structure acre 0 1 2 3 4 0 l 2 3 '4 0 1 2 3 50%WP... $6 75 13 78 22 80 95 85 80 100 CO-E N-NH 1 88 63 78 33 100 100 100 95 100 89 110 100 90 50%WP--- Cl $5 13 25 56 0. 75 80 75 30 25 1 100 50 89 0......100 90 80 90 55 45 75 10 0 JEN 01 507 WP--- y 50 e2 56 -c0-E=N-NH J1 1 100 100 89 100 100 67 30 100 100 90 100 100 C O-C=N-NH -C l 1 100 100 100 33 100 100 100 95 100 100 100 100 90 100 50 89 11 100 100 100 100 100 C1 COZ=N--NH Cl 1'100 100 14 70 100 100 100 100 100 EN 7 h Southern armyworrns small, used second instar, not third.

13 EXAMPLE 44 Field Evaluation of Test Compound Test materials were applied at the rate of one pound actual ingredient in 57 gallons of water per acre. Application was made by a C power-pack sprayer with three flat-tip spray nozzles at a pressure of psi. and at a tractor speed of 4 miles per hour. The foliage of sixtyfoot rows of potatoes were treated on schedule for control 10 Armyworms of Colorado Potato Beetle (Leptinotarsa decemlineata).

14 EXAMPLE 46 Effectiveness of test compounds against insects of the order Coleoptera is shown in the following test.

The test procedure employed to determine the etficacy of compounds of the present invention for controlling insects of the order Coleoptera is the same as that described above for the Southern Armyworm which are of the order Lepidoptera, excepting that cucumber beetles and Mexican bean beetles are substituted for Southern Data obtained are reported in Table XI below.

TABLE XI [Use of several phenylhydraaones against adult spotted cucumber beetle (Diabiotico undeczmpunctata hcwurdz) and adult Mexican bean beetle (Epilachna vnriveatisfl Concen- Adult Adult tration Spotted Mexican in cucumber bean Structure p.p.m. beetles 1 beetle BEN Cl ,000 80 50 G N I CH: 01 1.000 80 50 G N l 2-day mortality data. I 4day mortality data.

EXAMPLE 47 The data obtained for the test compound and untreated 40 control are set forth in Table =IX below.

Procedure for small scale field trials for compounds of the present invention on corn is as follows. The ex- EXAMPLE The eifectiveness of the phenylhydrazone in the control of Imported Cabbage Worm (Pieris rapae) on thirty-one foot rows of cabbage was determined using the application procedure of Example 44. The results obtained are perimental materials were applied at the rate of 1 lb. actual ingredient in gallons of water per acre. Application was made by a portable compression sprayer at the speed of normal walking. Six feet by fourteen feet plots replicated three times were treated three times on a weekly schedule. Ten corn plants per plot were ex- (nntml 4, 1

. set forth in Table X below. amined for fall armyworms (Spodoptera frugiperda) TABLE X N o. of WOX'IIIS per Formnhead of Treatment Structure lation cabbage schedule 0 N 50% WP- 1. 0 4 applications, 7-day schedule.

wherein R is halo, alkyl of to 4 carbons, alkoxy of l 40 to 4 carbons, cyano, nitro, trifiuoromethyl or p-chlorophenoxy; R yis hydrogen, halo, trifluorornethyl or alkyl of 1 to 4 carbons; R is Z-furyl; and R is hydrogen or halo.

The results obtained are set forth in Table XII below.

TABLE XII [Use of phenylhydrazones in foliar treatment in field control of the fall armyworm (Spodoptera jrugipenia) on corn] Rate pounds Total actual worms ingredient in three Formuper repli- Strueture lation acre cates (iJ N 50% WP. 1 76 Cl 50% WP-.- 1 19 Goo-0:114:11:-

C EN 50% WP 1 26 Contr l 88 We claim: 0 1. A method for controlling insects comprising apply- 25 IL 0 ing to said insects an insecticidally effective amount of a compound of the formula:

B wherein R is halo, alkyl of 1 to 4 carbons, alkoxy of 1 to 4 carbons, cyano, nitro, trifiuoromethyl or p-chlorophenoxy.

6. An insecticidal composition comprising a suitable amount of a compound of Claim '1. 7

References Cited UNITED STATES PATENTS 9/1964 Urbschat et al 260-193 11/1964 Addor et al 260-465 OTHER REFERENCES I Dubenko et al.,'zh. Org. Khim, Vol. 5, No. 3, pp. 517-20, March 1969. 1 

1. A METHOD FOR CONTROLLING INSECTS COMPRISING APPLYING TO SAID INSECTS AN INSECTICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA: 